Method and system for forming plug and play metal compound catalysts

ABSTRACT

A metal compound catalyst is formed by vaporizing a quantity of catalyst material and a quantity of carrier thereby forming a vapor cloud, exposing the vapor cloud to a co-reactant and quenching the vapor cloud. The nanoparticles are impregnated onto supports. The supports are able to be used in existing heterogeneous catalysis systems. A system for forming metal compound catalysts comprises means for vaporizing a quantity of catalyst material and a quantity of carrier, quenching the resulting vapor cloud, forming precipitate nanoparticles comprising a portion of catalyst material and a portion of carrier, and subjecting the nanoparticles to a co-reactant. The system further comprises means for impregnating the of supports with the nanoparticles.

CROSS-REFERENCE TO RELATED APPLICATIONS

This patent application is a continuation application of U.S. patent application Ser. No. 14/010,392, filed Aug. 26, 2013, which is a continuation application of U.S. patent application Ser. No. 12/001,602, filed Dec. 11, 2007 (issued on Nov. 5, 2013 as U.S. Pat. No. 8,575,059), which claims priority benefit of U.S. Provisional Patent Application No. 60/999,057, filed Oct. 15, 2007, the entire contents of each of which are hereby incorporated by reference herein.

BACKGROUND OF THE INVENTION

In the oil refining and fine chemical industries, catalysts are required to transform one chemical or one material into another. For example, to make cyclohexane from benzene, benzene is passed through porous ceramic supports that have been impregnated with catalysts designed and configured to hydrogenate it into cyclohexane. In one particular process, platinum is nitrated and impregnated onto supports in the wet chemical process 100 shown in FIG. 1. A platinum group metal, such as platinum, osmium, ruthenium, rhodium, palladium or iridium, is collected in step 101. For the sake of brevity, platinum will be discussed herein but it will be apparent to those of ordinary skill in the art that different platinum group metals can be used to take advantage of their different properties. Since blocks of elemental platinum are not useable as a catalyst, the platinum is nitrated in the step 102, forming a salt, specifically PtNO₃. The nitration is typically performed using well known methods of wet chemistry. The PtNO₃ is dissolved into a solvent such as water in a step 103, causing the PtNO₃ to dissociate into Pt+ and NO₃− ions. In the step 104, the salt is adsorbed onto the surfaces of supports 104B through transfer devices 104A, such as pipettes. An example of a support 104B is shown in FIG. 2. Generally, a support 104B is a highly porous ceramic material that is commercially available in a vast array of shapes, dimensions and pore sizes to accommodate particular requirements of a given application. The supports 104B are dried to remove water then transferred to an oven for an air calcining step 105. In the oven, the supports 104B are exposed to heat and optionally pressure that causes the Pt+ to coalesce into elemental Pt particles on the surfaces of the supports 104B. In the step 106, end product catalysts are formed. The end product is a support 104B that is impregnated with elemental platinum. These supports are generally used in catalytic conversion by placing them in reactors of various configurations. For example, benzene is passed through the supports 104B which convert the benzene into cyclohexane in the fine chemical industry. In the oil refining industry, the supports are used in a similar fashion. The process steps are used to convert crude oil into a useable fuel or other desirable end product. The process described in FIG. 1 has opportunities for improvement. Although the platinum sticks sufficiently well to the surface of the support 104 b, platinum atoms begin to move and coalesce into larger particles at the temperatures that catalysis generally occurs. It is understood that the effectiveness and activity of a catalyst are directly proportional to the size of the catalyst particles on the surface of the support. As the particles coalesce into larger clumps, the particle sizes increase, the surface area of the catalyst decreases and the effectiveness of the catalyst is detrimentally affected. As the effectiveness of the catalyst decreases, the supports 104B must be removed from the reactors and new supports added. During the transition period, output is stopped and overall throughput is adversely affected. Also, platinum group metal catalysts are very expensive, and every addition of new supports comes at great cost. What is needed is a plug and play catalyst that is usable in current oil refineries and fine chemical processing plants, allowing an increase in throughput and decrease in costs.

SUMMARY OF THE INVENTION

A method of making a metal compound catalyst comprises providing a quantity of nanoparticles, wherein at least some of the nanoparticles comprise a first portion comprising catalyst material bonded to a second portion comprising a carrier, providing a quantity of supports; and impregnating the supports with the nanoparticles. In some embodiments, the supports comprise pores and voids. The catalyst material comprises any among a list of at least one metal, at least one metal alloy, and any combination thereof. Also, the catalyst material comprises any among a list of nitrogen, carbon, phosphorous, hydrogen, oxygen, sulfur, and any combination thereof. Preferably, providing a quantity of nanoparticles comprises loading a quantity of catalyst material and a quantity of carrier into a plasma gun in a desired ratio, vaporizing a quantity of catalyst and quantity of carrier, thereby forming a vapor cloud quenching the vapor cloud, thereby forming precipitate nanoparticles, and injecting a co-reactant such that the co-reactant will react with one of the vapor cloud, the first portion of the precipitate nanoparticles and any combination thereof. The co-reactant is injected into a substantially low oxygen environment. The co-reactant comprises any among a list of a carbon compound, a nitrogen compound, a phosphorous compound, and oxygen compound, a hydrogen compound, a sulfur compound, and any combination thereof. Preferably, the carrier comprises an oxide such as silica, alumina, yttria, zirconia, titania, ceria, baria, and any combination thereof. Preferably, impregnating the supports comprises suspending the nanoparticles in a solution, thereby forming a suspension, and mixing the suspension with a quantity of the supports. Alternatively, impregnating the supports comprises suspending the nanoparticles in a solution, thereby forming a suspension, and mixing the suspension with a slurry having supports suspended therein. The slurry comprises any among an organic solvent, an aqueous solvent, and a combination thereof. Preferably, the method further comprises drying the supports. The method further comprises exposing the supports to any one of heat, pressure or a combination thereof, thereby calcining the nanoparticles onto the supports.

A system for forming a metal compound catalyst comprises means for providing a quantity of nanoparticles, wherein at least some of the nanoparticles comprise a first portion of catalyst material bonded to a second portion of carrier, means for collecting the nanoparticles, means for forming a suspension by mixing the nanoparticles into a liquid, and means for combining the suspension with a quantity of supports, thereby supports with the dispersion. Preferably, the catalyst material comprises any among a list of at least one metal, at least one metal alloy, and any combination thereof. Also, the catalyst material comprises any among a list of nitrogen, carbon, phosphorous, hydrogen, oxygen, sulfur, and any combination thereof. Preferably, the means for providing a quantity of nanoparticles comprises means for loading a quantity of catalyst material and a quantity of carrier into a plasma gun in a desired ratio means for vaporizing the quantity of catalyst material and carrier material in a reaction chamber, thereby forming a reactant vapor cloud means for quenching the reactant vapor cloud thereby forming solid nanoparticles, and means for injecting a co-reactant such that the co-reactant will react with any among the vapor cloud, the first portion of the nanoparticles, and any combination thereof. Preferably, the means for injecting a co-reactant comprises means for injecting the co-reactant into a substantially low oxygen environment. The co-reactant comprises any among a list of a carbon compound, a nitrogen compound, a phosphorous compound, an oxygen compound, a hydrogen compound, and any combination thereof. The system further comprises means for drying the supports. Preferably, the system further comprises means for exposing the supports to any among heat, pressure, and a combination thereof thereby calcining the nanoparticles onto the supports. Preferably, means for combining the suspension with supports comprises means for impregnating supports with the suspension. Alternatively, the means for combining the suspension with supports comprises means for mixing the suspension with a slurry having supports. The slurry comprises any among an organic solvent, an aqueous solvent, and any combination thereof.

BRIEF DESCRIPTION OF THE DRAWINGS

The invention is better understood by reading the following detailed description of an exemplary embodiment in conjunction with the accompanying drawings.

FIG. 1 prior art illustrates an existing process for forming a useful support for use in heterogenous catalysis.

FIG. 2 prior art shows a porous support generally used as a support in heterogeneous catalysis.

FIG. 3 shows the preferred embodiment of a novel process for forming a support for use in heterogeneous catalysis.

FIG. 4A shows an example of a nanoparticle formed as part of the process of FIG. 3.

FIG. 4B shows a close up of an impregnated porous support.

FIG. 4C shows a close up of an impregnated macro support.

FIG. 5 shows an example of the supports being used as heterogeneous catalysts.

FIG. 5A shows the hydrogenation of benzene into cyclohexane.

DETAILED DESCRIPTION OF THE INVENTION

Reference will now be made in detail to implementations of the present invention as illustrated in the accompanying drawings. The drawings may not be to scale. The same reference indicators will be used throughout the drawings and the following detailed description to refer to identical or like elements. In the interest of clarity, not all of the routine features of the implementations described herein are shown and described. It will, of course, be appreciated that in the development of any such actual implementation, numerous implementation-specific decisions must be made in order to achieve the developer's specific goals, such as compliance with application, safety regulations and business related constraints, and that these specific goals will vary from one implementation to another and from one developer to another. Moreover, it will be appreciated that such a development effort will be a routine undertaking of engineering for those of ordinary skill in the art having the benefit of this disclosure.

The following description of the invention is provided as an enabling teaching which includes its best currently known embodiment. One skilled in the relevant arts, including but not limited to chemistry and physics, will recognize that many changes can be made to the embodiment described, while still obtaining the beneficial results of the present invention. It will also be apparent that some of the desired benefits of the present invention can be obtained by selecting some of the features of the present invention without utilizing other features. Accordingly, those who work in the art will recognize that many modifications and adaptations to the present inventions are possible and may even be desirable in certain circumstances, and are a part of the present invention. Thus, the following description is provided as illustrative of the principles of the present invention and not in limitation thereof, since the scope of the present invention is defined by the claims. The terms “nanoparticle,” “nanoparticle powder,” and “nano powder” are generally understood by those of ordinary skill to encompass a quantity of material comprising particles on the order of nanometers in diameter, as described herein. The term “metal compound” is generally understood by those of ordinary skill to encompass a compound comprising at least one metal and at least one non metal.

FIG. 3 illustrates the inventive steps for a process 300 of forming a “plug and play” catalyst for use in such industries as chemical manufacturing and oil refining. The method begins at the step 310. A quantity of a catalyst material 312 is loaded into a plasma gun 315. Preferably, the catalyst material 312 comprises a transition metal. Transition metals (TM) and their compounds are able to provide excellent catalytic properties. Although transition metals are described, all metals are contemplated. Other metals, such as platinum group metals and poor metals, also exhibit catalytic properties. Generally, transition metals comprise scandium, titanium, chromium, vanadium, manganese, iron, cobalt, nickel, copper, zinc, yttrium, zirconium, niobium, molybdenum, cadmium, tantalum, tungsten, and mercury. Poor metals comprise aluminum, germanium, gallium, tin, antimony, lead, indium, tellurium, polonium and bismuth. Platinum group metals comprise ruthenium, rhodium, palladium, osmium, iridium, and platinum. The catalyst material 312 is able to comprise more than one starting metal. By way of example, the material 312 is a single alloy comprising multiple metals. Alternatively, the catalyst material 312 comprises multiple homogenous metals or metal compounds such as oxides. Particularly, metals are used in heterogeneous catalysis. Heterogeneous catalysts provide a surface for the chemical reaction to take place on or provide an activation point for chemical reactions. Also, in step 310, a quantity of carrier material 314 is loaded into the plasma gun 315. In some embodiments, the carrier material 314 is an oxide. By way of example, oxides such as Alumina (Al₂O₃), Silica (SiO₂), Zirconia (ZrO₂), Titania (TiO₂), Ceria (CeO₂) Baria (BaO), and Yttria (Y₂O₃) can be used. Other useful oxides will be apparent to those of ordinary skill. In some embodiments, the catalyst material 312 and carrier material 314 are loaded manually into a hopper (not shown) which automatically loads the materials into the plasma gun 315. In alternate embodiments, an automated system is able to load the catalyst material 312 and oxide carrier 314 into the plasma gun 315. The ratio of the TM to the carrier can be adjusted to meet particular demands of a given application. Next, in step 320, the plasma gun 315 vaporizes the catalyst material 312 along with the carrier 314 to form a vapor cloud 325. The vapor cloud will comprise both the catalyst material, for example TM, and the carrier in the ratio that was loaded into the plasma gun 315 in step 310.

Still referring to FIG. 3, the resulting vapor cloud 325 is then put through a quenching step 330. Preferably, the quenching step occurs in a highly turbulent quench chamber 327 to facilitate rapid, even, consistent quenching of the vapor cloud 325 into precipitate nanoparticles. Such a rapid quench chamber is described in detail in U.S. patent application Ser. No. 12/151,935 (US 2008/0277267), and is hereby incorporated by reference. As the gaseous TM and carrier cool, they solidify into nanoparticles. An example of a resulting nanoparticle 400 is shown in FIG. 4A. As shown, the nanoparticle comprises a portion of carrier 410, and a portion of TM catalyst 420. The ratio of size between the TM catalyst 420 and carrier 410 will generally be determined by the ratio of the starting quantities of catalyst material 312, such as TM and carrier material 314 in the step 310 of FIG. 3. To further enhance the catalytic effects of the TM, the TM is combined with a nonmetal to form a metal compound. Preferably, the combination is effectuated by injecting a co-reactant, in this example a co-reactant gas 337 into the reaction chamber 327. Preferably, the co-reactant 337 is injected as a gas post plasma. In some embodiments, the injected gas 337 is organic. Alternatively, the injected gas is an oxygen compound, a hydrogen compound, a nitrogen compound, a phosphorous compound, a sulfur compound, or a carbon containing compound. Preferably, as the particles 400 precipitate, the gas 337 dissociates into its component elements that then react with the metal portion 420 of the nanoparticle 400. Alternatively, a chemical reaction occurs between the gas to the metal portion 420 of the nanoparticle 400. As described, the gas 337 interacts with the metal portion 420 of the nanoparticles 400 after the nanoparticles have precipitated from the vapor cloud 325. Interaction between the gas 337 and the vapor cloud 325 itself is also contemplated. The gas 337 dissociates into its constituent elements which then react with the catalyst material 312 in its vapor state before precipitation. Alternatively, the gas 337 reacts with the catalyst material 312 without dissociating. It is understood the reaction of the gas 337 with the catalyst material 312 or metal portion 420 of the nanoparticle 400 is able to occur before, during, or after precipitation, or may begin before precipitation and complete after precipitation. By way of example, and not intended to be in any way limiting, if the end catalyst product desired is the metal compound tungsten carbide, the starting catalyst material 312 will be a quantity of tungsten. Along with a quantity of a carrier 314, such as alumina, the quantity of tungsten is loaded into the plasma gun 315. After vaporization, nanoparticles of tungsten will collide with nanoparticles of alumina and form the nanoparticles 400. Further down the reaction chamber 327 from the plasma gun 315, methane vapor 337 (CH₄) is injected. It is important to note that the methane vapor 337 is injected into the reaction chamber 327 where the temperature is sufficient to dissociate methane into its components, carbon and hydrogen. Alternatively, the methane reacts with the tungsten. As described above, the reaction is able to occur before, during, after, or throughout the precipitation of tungsten-on-alumina nanoparticles 400. Also, to avoid combustion of the methane into carbon dioxide and water, rather than elemental carbon and hydrogen, a substantially low oxygen environment is provided for the reaction chamber 327. A low oxygen reaction chamber is described in detail in U.S. patent application Ser. No. 12/961,200 (U.S. Pat. No. 9,119,309) and is hereby incorporated by reference. When the methane dissociates, the hydrogen atoms form hydrogen vapor. The carbon atom is known to be extremely reactive, and will carburize the tungsten forming tungsten carbide. Alternatively, a chemical reaction will react the methane to the tungsten. Referring to the example nanoparticle 400 in FIG. 4, the catalyst portion 420 is the metal compound tungsten carbide. It can be appreciated by those of ordinary skill in the art that other compound catalysts are able to be formed by the process 300. If a different metal compound, such as a metal nitride is the desired final product, the desired metal will be loaded into the plasma gun 315 and ammonia (NH₃) rather than methane will be injected into the reaction chamber 327. As ammonia dissociates into its constituent elements, they will react with the desired metal to form a metal nitride. It will be apparent to those of ordinary skill that many combinations of metals and nonmetals are able to be combined in the manner described, and the two examples given are not intended in any way to limit the scope of the disclosure. As new catalysts are required for new chemical processes, the process 300 is able to be applied through a routine, although possibly time consuming engineering endeavor. The particles 400 will generally be in the range of 0.5 to 200 nm in size, and can be as small as a molecular length of the catalyst portion 420 and as large as would be achievable by ball milling. The particle size is able to be varied with varying starting materials, vaporization speeds, quench speeds and plasma temperatures.

U.S. Pat. No. 5,989,648 to Phillips discloses a method for forming nanoparticle metal catalysts on carriers. However, referring back to FIG. 3, it is important to note that nanoparticles 400 such as the one shown in FIG. 4 are not generally compatible with existing processes for chemical conversion. For compatibility with existing processes, the nanoparticles 400 are bonded to a support. To that end, more steps are taken to bring the nanoparticles 400 to a useable form. In some embodiments, the process 300 continues with step 340, where the nanoparticles 400 are combined with a liquid to form a dispersion 345. Preferably, a liquid that will not react with the TM or the carrier material is used. Some appropriate liquids are aqueous solutions or organic solutions employing solvents such as alcohols, ethers, hydrocarbons, esters, amines, or the like. Since the nanoparticles 400 are small, other precautions are generally taken to ensure that they suspend evenly within the dispersion. To that end, an adjunct 348 is able to be added to the dispersion. The adjunct 348, also referred to commonly in the art as a surfactant or dispersant, adheres to the nanoparticles 400 and causes them to repel each other, thereby causing the nanoparticles 400 to suspend evenly in the dispersion 345. The dispersion 345 is also referred to as a suspension.

To bring the nanoparticles 400 closer to a usable catalyst, the nanoparticles 400 are impregnated onto supports 355. The supports 355 are also known to those skilled in the relevant art as porous oxides. Alternatively, the supports 355 are also referred to as extrudates because they are generally made using an extrusion process. The supports 355 are similar to the supports 104 b in FIGS. 1 and 2. Such supports have found utility due to their highly accessible and large surface area, as high as 250 m²/g. In alternative embodiments, a macroscopic support particle is able to be used. In such an embodiment, the size of the macroscopic support particle is selected to provide maximum surface area to which nanoparticles 400 are bonded or fixed. The step 350A shows the preferred embodiment of achieving the impregnation. The dispersion 345 is combined with a quantity of substantially dry porous supports 355A to form a mixture 359A. Alternatively, as shown in the step 350B, the dispersion 345 is combined with a slurry 358 having macroscopic support particles 355B suspended therein, thereby forming the mixture 359B. The slurry 358 is able to be a suspension of water, alcohol, or any suitable organic or inorganic liquid which will not react with the macroscopic supports 355B or nanoparticles 400. In the step 350A, capillary forces will draw in the dispersion 345, and in turn the nanoparticles 400, into the various voids and pores within the structure of the porous supports 355A, thereby forming impregnated porous supports 365A. To aid in the impregnation, the mixture can be agitated or subjected to heat or pressure. In the step 350B, nanoparticles 400 come to rest on the surfaces of macroscopic supports thereby forming impregnated macro supports 365B. In some embodiments, the steps 350A or 350B are repeated at least once for enhanced impregnation.

Next, in the steps 360A and 360B, the impregnated porous supports 365A or macro supports 365B are allowed to dry. A close up view the impregnated porous support 365A is shown in FIG. 4B. As the liquid in the dispersion 345 evaporates, the nanoparticles 400 settle onto the surface of the support 365A and into the pores 367 within the support 365A. FIG. 4C shows an example of an impregnated macro support 365B. As the liquids in the dispersion 345 and slurry 358 dry, nanoparticles 400 settle onto the surface of the macro support 365B. When the impregnated porous supports 365A or macro supports 365B dry, electrostatic interactions and other non covalent forces between the nanoparticles 400 and the porous supports 365A or macro supports 365B effectuate some adhesion. Advantageously, such forces cause the nanoparticles 400 to stick onto the surfaces and pores 367 of the supports 365A or 365B, and effectuate transfer of the supports 365 through the remainder of the process 300. Referring back to FIG. 3, a calcining step 370A or 370B is performed to form oxide-oxide bonds between the carrier portion 410 of the nanoparticles 400 and the impregnated supports 365A or 365B by exposing them to heat 372, pressure 375, or a combination thereof. The calcining temperature is generally from 350 to 1000 degrees centigrade, and the pressure is on the order of ambient atmosphere to several atmospheres. Calcining is able to occur in an inert environment or in air. For optimum oxide-oxide bonds, the carrier material 314 is chosen to correspond to the material of which the support 365A or 365B is comprised. By way of example, if the carrier material 314 is alumina, then the support 365A or 364B preferably comprises alumina, although dissimilar oxides are also contemplated. Due to the physical and chemical bond between the supports 365A and 365B and the nanoparticles 400, islands of nanoparticles that are bonded, fixed or otherwise pinned to the surfaces of the supports 365A or 365B will not migrate and coalesce during catalytic conversion. The surface area for catalysis remains high, and therefore the catalytic activity remains high. In effect, operations such as fine chemical plants and oil refineries will not be required to stop operations and swap out ineffective catalyst supports with fresh catalyst supports with the same frequency as existing processes, thereby increasing throughput at the plants and refineries and reducing their overall cost of operation.

FIG. 5 shows an example of the impregnated porous supports 365A being used in the fine chemical industry to hydrogenate benzene into cyclohexane. Macro supports 365B are able to be used as well. Although this example details use in the fine chemical industry, it will be apparent to those of ordinary skill in the arts of chemistry, chemical engineering, or the like that any process using heterogeneous catalysis is able to benefit from this disclosure. An amount of impregnated porous supports 365A is loaded into a reactor 510. Preferably, the reactor 510 has a mesh opening 515 on one end wherein the meshing has a smaller opening pitch than the size of the supports 365 such that the supports 365 do not fall through the opening 515. Benzene is passed into the vat 510 via the conduit 520. As the benzene passes through the vat 510, the benzene fills into the voids and pores of the supports 365A.

FIG. 5A shows an example of a benzene molecule 525 being hydrogenated into cyclohexane 525A in a cross section of a pore 367. When the benzene molecule 525 comes into contact with the catalyst portion 420 of the nanoparticle 400 that is bonded to the surface of the support 365A, the catalyst portion 420 of the nanoparticle 400 will effectuate hydrogenation of the benzene molecule 525 and hydrogen molecules 525B into cyclohexane 525A. 

We claim:
 1. A supported catalyst, comprising: a. a support structure comprising an oxide, b. a nanoparticle wherein the nanoparticle has been reacted with a co-reactant, comprising: i) a catalyst portion, and ii) a carrier portion, said carrier portion comprising an oxide; wherein the carrier portion is bonded to the support structure through an oxide-oxide bond.
 2. The supported catalyst of claim 1 wherein the catalyst portion comprises a material selected from the group consisting of a metal, a metal compound, a metal alloy, and any combination thereof.
 3. The supported catalyst of claim 1 wherein the oxide carrier portion comprises a material selected from the group consisting of silica, alumina, yttria, zirconia, titania, ceria, baria, and any combination thereof.
 4. The supported catalyst of claim 1, wherein the oxide carrier portion comprises alumina.
 5. The supported catalyst of claim 1, wherein the oxide carrier portion comprises ceria.
 6. The supported catalyst of claim 1, wherein the catalyst portion comprises a transition metal.
 7. The supported catalyst of claim 1, wherein the catalyst portion comprises a platinum group metal.
 8. The supported catalyst of claim 1, wherein the catalyst portion comprises platinum.
 9. The supported catalyst of claim 1, wherein the catalyst portion comprises palladium.
 10. The supported catalyst of claim 1, wherein the catalyst portion comprises rhodium.
 11. The supported catalyst of claim 1, wherein the co-reactant comprises a reactant selected from the group consisting of a carbon compound, a nitrogen compound, a phosphorus compound, an oxygen compound, a hydrogen compound, a sulfur compound, and any combination thereof.
 12. The supported catalyst of claim 1, wherein the support structure comprises a porous oxide.
 13. The supported catalyst of claim 1, wherein the support structure comprises alumina.
 14. The supported catalyst of claim 1, wherein the catalyst portion comprises a platinum group metal, the oxide carrier portion comprises alumina, and the support structure comprises alumina.
 15. The supported catalyst of claim 1, wherein the catalyst portion comprises platinum, the oxide carrier portion comprises alumina, and the support structure comprises alumina.
 16. The supported catalyst of claim 1, wherein the catalyst portion comprises palladium, the oxide carrier portion comprises alumina, and the support structure comprises alumina.
 17. The supported catalyst of claim 1, wherein the catalyst portion comprises rhodium, the oxide carrier portion comprises alumina, and the support structure comprises alumina. 